KR20180018819A - The perfluoro (poly) ether group-containing silane compound - Google Patents

Abstract

[식 중, 각 기호는 명세서 중의 기재와 같은 의미임.]로 표현되는 퍼플루오로(폴리)에테르기 함유 실란 화합물.Formula (1a) or Formula (1b):

(Poly) ether group-containing silane compound represented by the following formula: wherein each symbol is as defined in the specification.

Description

The perfluoro (poly) ether group-containing silane compound

The present invention relates to a perfluoro (poly) ether group-containing silane compound.

It is known that any kind of fluorine-containing silane compound can provide excellent water repellency, oil repellency, and antifouling property when used in the surface treatment of a substrate. A layer obtained from a surface treatment agent containing a fluorine-containing silane compound (hereinafter also referred to as a " surface treatment layer ") is a so-called functional thin film applied to various substrates such as glass, plastic, fiber and building materials.

As such a fluorine-containing compound, a perfluoropolyether group-containing silane compound having a perfluoropolyether group in its molecular backbone and a hydrolyzable group bonded to a Si atom at a molecular end or a terminal portion is known (see Patent Documents 1 to 3) 2).

Japanese Patent Publication No. 2008-534696 WO 97/07155

The surface treatment layer is required to have a high durability in order to provide a desired function to a substrate over a long period of time. The layer obtained from a surface treatment agent containing a perfluoropolyether group-containing silane compound is suitable for an optical member such as a glass or a touch panel in which light transmittance or transparency is required since the above function can be exhibited also in a thin film In particular, in these applications, a further improvement in friction durability is required.

However, in the layer obtained from the surface treatment agent containing the conventional perfluoropolyether group-containing silane compound as described above, it is not always sufficient to satisfy the requirement for the improvement of the friction durability which is gradually increased.

It is an object of the present invention to provide a novel perfluoro (poly) ether group-containing silane compound capable of forming a layer having water repellency, oil repellency, antifouling property and high friction durability.

As a result of intensive studies, the present inventors have found that the friction durability of a surface treatment layer is improved by using a perfluoropolyether group-containing silane compound having a plurality of Si atoms each having a hydrolyzable group, It came.

That is, according to the first aspect of the present invention, in formula (1a) or (1b):

[Wherein:

Rf represents, independently at each occurrence, an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;

PFPE is independently present at each occurrence of the formula:

A, b, c, and d are each independently an integer of 0 to 200, and the sum of a, b, c, and d is at least 1 and is in parentheses The order of existence of each repeating unit is arbitrary in the formula.)

≪ / RTI >

Each X independently represents a single bond or an organic group of 2 to 10 carbon atoms;

a is independently an integer of 1 to 9;

beta is an integer from 1 to 9;

R ^a independently for each occurrence represents -Z-CR ¹ _p R ² _q R ³ _r ;

Z represents, at each occurrence independently of each other, an oxygen atom or a divalent organic group;

R ¹ represents each independently a, R ^{a ',} in each occurrence;

R ^{a '} has the same meaning as R ^a ;

Of R &^lt; a >, there are at most 5 C connected in a straight chain through the group Z;

R ² for each occurrence independently represents -Y-SiR ⁵ _n R ⁶ _{3 -n} ;

Y represents, independently at each occurrence, a divalent organic group;

R < ⁵ > independently at each occurrence represents a hydroxyl or hydrolyzable group;

R ⁶ represents, independently at each occurrence, a hydrogen atom or a lower alkyl group;

n is the (-Y-SiR ⁵ R ⁶ _{n 3 -n)} independently for each unit, an integer of 1 to 3;

R ³ represents, independently at each occurrence, a hydrogen atom or a lower alkyl group;

p is, independently at each occurrence, an integer from 0 to 3;

q is, independently at each occurrence, an integer from 0 to 3;

r is, independently at each occurrence, an integer from 0 to 3;

R ^b for each occurrence independently represents -Y-SiR ⁵ _n R ⁶ _{3 -n} ;

R ^c each independently represent a hydrogen atom or a lower alkyl group at each occurrence;

k is, independently for each occurrence, an integer from 0 to 3;

l is independently at each occurrence an integer of 0 to 3;

m is, independently at each occurrence, an integer from 0 to 3;

With the proviso that at least one q is 2 or 3, or at least one l is 2 or 3. < RTI ID = 0.0 >

(Poly) ether group-containing silane compound expressed by the following general formula (1).

According to a second aspect of the present invention, there is provided a surface treating agent containing the perfluoro (poly) ether group-containing silane compound.

According to a third aspect of the present invention, there is provided a pellet containing the surface treatment agent.

According to a fourth aspect of the present invention, there is provided an article comprising a base material and a layer formed of the perfluoropolyether group-containing silane compound or the surface treatment agent on the surface of the base material.

According to the present invention, a novel perfluoro (poly) ether group-containing silane compound is provided. Further, a surface treating agent obtained by using the perfluoro (poly) ether group-containing silane compound of the present invention is provided. By using them, a surface treatment layer having water repellency, oil repellency, antifouling property and excellent light resistance can be formed.

Hereinafter, the compounds of the present invention will be described.

As used herein, the term " hydrocarbon group " means a group containing carbon and hydrogen, and means a group in which one hydrogen atom has been removed from a hydrocarbon. Such a hydrocarbon group is not particularly limited, but may be a hydrocarbon group having 1 to 20 carbon atoms, which may be substituted with one or more substituents, such as an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The "aliphatic hydrocarbon group" may be any of linear, branched or cyclic, and may be either saturated or unsaturated. In addition, the hydrocarbon group may contain one or more ring structures. Such a hydrocarbon group may have one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy and the like in its terminal or molecular chain.

As used herein, the substituent of the "hydrocarbon group" is not particularly limited and includes, for example, a halogen atom; 1 or that may be substituted by more halogen atoms, C _{1- 6} alkyl, C _{2- 6} alkenyl, C _{2- 6} alkynyl, C _{3- 10} cycloalkyl group, a C _3-10 unsaturated cycloalkyl group, 5 A 5- to 10-membered heterocyclyl group, a 5- to 10-membered unsaturated heterocyclyl group, a C _{6 -10} aryl group and a 5- to 10-membered heteroaryl group.

As used herein, the term "organic group" means a group containing carbon. The organic group is not particularly limited, but may be a hydrocarbon group. Further, the "2 to 10-valent organic group" means a 2 to 10-valent group containing carbon. Such a 2 to 10-valent organic group is not particularly limited, but a 2 to 10-valent group in which 1 to 9 hydrogen atoms are further eliminated from a hydrocarbon group can be exemplified. For example, the divalent organic group is not particularly limited, but a divalent group obtained by removing one hydrogen atom from a hydrocarbon group can be exemplified.

The present invention provides a silane compound containing perfluoro (poly) ether group (hereinafter also referred to as " PFPE ") represented by formula (1a) or formula (1b) "Sam Browne).

In the formula, Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.

The "alkyl group having 1 to 16 carbon atoms" in the alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms may be straight chain or branched chain, 1 to 6, particularly 1 to 3 carbon atoms, and more preferably a straight-chain alkyl group having 1 to 3 carbon atoms.

The Rf is preferably an alkyl group having 1 to 16 carbon atoms which is substituted by one or more fluorine atoms, more preferably a CF ₂ HC _{1- 15} fluoroalkylene group, still more preferably 1 to 16 carbon atoms Perfluoroalkyl group.

The perfluoroalkyl group having 1 to 16 carbon atoms may be a straight chain or branched chain, preferably a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, more preferably a straight chain or branched chain A perfluoroalkyl group having 1 to 3 carbon atoms, specifically -CF ₃ , -CF ₂ CF ₃ or -CF ₂ CF ₂ CF ₃ .

In the formula, PFPE is _{- (OC 4 F 8) a} - corresponds, and perfluoro (poly) ether groups _{- (OC 3 F 6) b} - (OC 2 F 4) c - (OCF 2) d. Here, a, b, c and d are each independently 0 or an integer of 1 or more, and the sum of a, b, c and d is at least 1. Preferably, a, b, c and d are each independently an integer of 0 or more and 200 or less, for example, an integer of 1 to 200, and more preferably an integer of 0 or more and 100 or less, Lt; / RTI > The sum of a, b, c and d is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 200 or less. In addition, the order of existence of each repeating unit in a, b, c, or d and enclosed in parentheses is arbitrary in the formula. Of these repeating _{units, - (OC 4 F 8)} - it is _{- (OCF 2 CF 2 CF 2} CF 2) -, - (OCF (CF 3) CF 2 CF 2) -, - (OCF 2 CF (CF 3) _{CF 2) -, - (OCF} 2 CF 2 CF (CF 3)) -, - (OC (CF 3) 2 CF 2) -, - (OCF 2 C (CF 3) 2) -, - (OCF (CF _{3) CF (CF 3))} -, - (OCF (C 2 F 5) CF 2) - and _{- (OCF 2 CF (C 2} F 5)) - of which one, but even if, preferably, - (OCF ₂ CF ₂ CF ₂ CF ₂ ) -. - (OC ₃ F ₆₎ - is _{- (OCF 2 CF 2 CF 2} ) -, - (OCF (CF 3) CF 2) - and _{- (OCF 2 CF (CF 3} )) - which is, but even if the, preferably Is - (OCF ₂ CF ₂ CF ₂ ) -. Further, - (OC ₂ F ₄ ) - may be - (OCF ₂ CF ₂ ) - and - (OCF (CF ₃ )) -, but is preferably - (OCF ₂ CF ₂ ) -.

In one form, PFPE is - (OC ₃ F ₆ ) _b - (wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, and more preferably 10 or more and 200 or less) (OCF ₂ CF ₂ CF ₂ ) _b - wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, or - (OCF (CF ₃ ) CF ₂ ) _b - wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, and more preferably 10 or more and 200 or less, and more preferably - (OCF ₂ CF ₂ CF ₂ ) _b - (wherein b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, and more preferably 10 or more and 200 or less).

In a further aspect, PFPE is _{- (OC 4 F 8) a} - (OC 3 F 6) b - (OC 2 F 4) c - (OCF 2) d - ( wherein, a and b are independently 0, respectively And c and d are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and subscripts a, b, c, or d, optionally in the presence order of the repeating units of formula bound to Im), preferably _{- (OCF 2 CF 2 CF 2} CF 2) a - (OCF 2 CF 2 CF 2) b - (OCF 2 CF 2) c - (OCF ₂ ) _d -. In one form, PFPE is - (OC ₂ F ₄ ) _c - (OCF ₂ ) _d - wherein c and d are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, Is an integer of 10 or more and 200 or less, and the order of existence of each repeating unit attached with a suffix c or d and parenthesized is arbitrary in the formula).

In one embodiment, the _{- (OC 4 F 8) a} - (OC 3 F 6) b - (OC 2 F 4) c - (OCF 2) d - in the ratio of c to d (hereinafter Quot; c / d ratio ") is 0.2, preferably 0.3, and the upper limit of the c / d ratio is 1.5, preferably 1.3, more preferably 1.1, By setting the c / d ratio to 1.5 or less, the slidability and the friction durability of the surface treatment layer obtained from the compound are further improved. As the c / d ratio is smaller, the slidability and the friction durability of the surface treatment layer are further improved. On the other hand, by setting the c / d ratio to 0.2 or more, the stability of the compound can be further increased. The greater the c / d ratio, the better the stability of the compound.

In another aspect, PFPE is a group represented by - (OC ₂ F ₄ -R ⁸ ) _{n "} -, wherein R ⁸ is selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ Or a combination of two or three groups independently selected from these groups. As the combination of two or three groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , But are not limited to, -OC ₂ F ₄ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₄ F ₈ -, -OC ₃ F ₆ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₃ F ₆ - , -OC ₃ F ₆ OC ₄ F ₈ -, -OC ₄ F ₈ OC ₄ F ₈ -, -OC ₄ F ₈ OC ₃ F ₆ -, -OC ₄ F ₈ OC ₂ F ₄ -, -OC ₂ F ₄ OC ₂ F ₄ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₂ F ₄ OC ₄ F ₈ -, -OC ₂ F ₄ OC ₃ F ₆ OC ₂ F ₄ -, -OC ₂ F ₄ OC ₃ F ₆ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₄ F ₈ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₂ F ₄ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₂ F ₄ OC ₃ F ₆ - -OC ₃ F ₆ OC ₃ F ₆ OC ₂ F ₄ - and -OC ₄ F ₈ OC ₂ F ₄ OC ₂ F ₄ -, etc. The above n "is an integer of 2 to 100, Lt; / RTI > In the formula, OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ may be either straight chain or branched chain, and preferably straight chain. In this form, the PFPE is preferably - (OC ₂ F ₄ -OC ₃ F ₆ ) _{n "} - or - (OC ₂ F ₄ -OC ₄ F ₈ ) _n" -.

Wherein each X independently represents a single bond or an organic group of 2 to 10 carbon atoms. X is a compound represented by formulas (1a) and (1b), and a perfluoropolyether moiety (i.e., Rf-PFPE moiety or -PFPE moiety) which mainly provides water repellency and surface slipperiness, (That is, a group bracketed with " a "). Accordingly, the X may be any organic group provided that the compound represented by the formulas (1a) and (1b) can be stably present.

Wherein? Is an integer of 1 to 9, and? Is an integer of 1 to 9. These? And? Can be changed according to the valence of X. In formula (1a), the sum of? And? Is equal to the valence of X. For example, when X is a 10-valent organic group, the sum of? And? Is 10, for example,? Is 9,? Is 1,? Is 5,? Is 5 or? 9 < / RTI > Further, when X is a divalent organic group,? And? In the equation (1b),? Is a value obtained by subtracting 1 from the mantissa of X.

X is preferably 2 to 7, more preferably 2 to 4, and most preferably a divalent organic group.

In one form, X is a 2- to 4-membered organic group,? Is 1 to 3, and? Is 1.

In another form, X is a divalent organic group,? Is 1, and? Is 1. In this case, the equations (1a) and (1b) are expressed by the following equations (1a ') and (1b').

Examples of the above X include, but are not particularly limited to,

- (R ³¹ ) _{p '} - (X ^a ) _q' -

[Wherein:

R ³¹ independently represents a single bond, - (CH ₂ ) _{s '} - or o-, m- or p-phenylene group, preferably - (CH ₂ ) _s'

s' is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, still more preferably 1 or 2,

X ^a represents - (X ^b ) _{l '} -,

X ^b are each independently at each occurrence -O-, -S-, o-, m- or p-phenylene group, -C (O) O-, -Si (R ³³ ) ₂ -, - _{^{(R 33) 2 O) m}} '-Si (R 33) 2 -, -CONR 34 -, -O-CONR 34 -, -NR 34 - , and - (CH _{2) n'} - group is selected from the group consisting of And,

R ³³ are each independently, phenyl, C _{1- 6} alkyl or C _{1- 6} represents an alkoxy, preferably a phenyl group or a C _{1- 6} alkyl, in each occurrence, and more preferably a methyl group,

R ³⁴ in each occurrence independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group)

m 'each independently represents an integer of 1 to 100, preferably an integer of 1 to 20, at each occurrence,

n 'each independently represent an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3 in each occurrence,

l 'is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3,

p 'is 0, 1 or 2,

q 'is 0 or 1,

Wherein at least one of p 'and q' is at least 1, the order of existence of each repeating unit in which p 'or q' is attached and is enclosed in parentheses is optional,

And the like. Here, R ³¹ and X ^a (typically a hydrogen atom of R ³¹ and X ^a) is substituted by one or more substituents selected from a fluorine atom, C _1- C ₃ alkyl group and an alkyl group with _{1- 3} fluoro .

Preferably, X is

Wherein R ³¹ has the same meaning as above.

Lt; / RTI >

More preferably, X is

Wherein s 'and t' have the same meanings as above.

to be.

Wherein X < ^c >

Wherein R ³³ , R ³⁴ and m 'are as defined above,

u 'is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3.]. X ^c is preferably -O-.

Wherein X ^d is

Wherein each symbol is as defined above.

.

More preferably, X is

Wherein each symbol is as defined above.

Lt; / RTI >

Even more preferably, X is

V is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably 2 to 3, and R < ³³ >, m ', s', t 'and u' An integer.]

to be.

- (C _v H _2v ) - may be straight chain or branched, for example, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH (CH ₃ ) CH (CH ₃₎ CH ₂ - can be.

The X group is a fluorine atom, C _{1- 3} alkyl group and C _{1- 3} fluoro is optionally substituted by one or more substituents selected from (preferably _1- C ₃ perfluoroalkyl group).

In another aspect, the X group includes, for example, the following groups:

Wherein R ⁴¹ is each independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms or a C _1-6 alkoxy group, preferably a methyl group;

D,

(Wherein R ⁴² represents, independently of each other, a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group)

, ≪ / RTI >

E is - (CH ₂ ) _n - (n is an integer from 2 to 6)

D binds to the PFPE of the molecular backbone, and E binds to the opposite group to PFPE.

Specific examples of X include, for example,

And the like.

In another form, X may each independently be an organic group having from 3 to 10 carbon atoms.

In this form, examples of X groups include the following groups:

[Wherein,

R ⁴¹ each independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms or a C _1-6 alkoxy group, preferably a methyl group;

For each X group, any of T may be substituted with one or more of the following groups that bind to the PFPE of the molecular backbone of formula (1a) and (1b)

[Wherein R ⁴² independently represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group].

, And some of the other T's are - (CH ₂ ) _{n "} groups bonded to a group opposite to the PFPE of the molecular backbone (ie, -CR ^a _k R ^b ₁ R ^c _{m in} formulas (1a) and (1b) - (where n "is an integer from 2 to 6) and, if present, the rest are each independently a methyl group, a phenyl group or a C _1-6 alkoxy group.

In the formula, R ^a indicates a respectively _{^{independently, -Z-CR 1 p R 2}} q R 3 r at each occurrence.

In the formulas, Z represents an oxygen atom or a divalent organic group in each occurrence independently of each other.

The Z is preferably a C _{1- 6} alkylene _{group, - (CH 2) g -O-} (CH 2) h - ( wherein, g is an integer, such as an integer from 1 to 6, from 0 to 6 and , h is an integer from 0 to 6, for example an integer of 1 to 6) or - phenylene - (CH _{2) i} - (wherein, i is an integer of from 0 to 6), more preferably C _{1- 3} alkylene group. These groups are, for example, fluorine atom, C _{1- 6} alkyl, C _{2- 6} alkenyl group and C are optionally _2- substituted by one or more substituents selected from ₆ alkynyl group.

In the formulas, R ¹ represents R ^{a '} in each occurrence independently of each other. R ^{a '} has the same meaning as R ^a .

In R ^a , up to 5 C atoms are connected in a straight line through Z group. That is, in the R ^a, R ¹ is at least one, if any, the number of C atoms present C atoms at least two are from a group Z in R ^a connection with a straight chain, but coupled to a straight chain through a such a Z is Up to five. In addition, the "number of C atoms connected in a linear chain through the Z group in R ^a " is equivalent to the number of -ZC- connected in a straight chain in R ^a .

For example, the following is an example in which a C atom is connected through the group Z in R ^a .

In the above formula, * denotes a bonding site to C of the main chain, Is that a predetermined group other than ZC is bonded, that is, all three bonding hands of C atoms are bonded to each other. , It means the end point of repetition of ZC. In addition, the number of the right shoulder of C means the number of occurrences of C directly connected through the Z group counted from *. In other words, numbered from C ² ZC repeat the chain that is terminated is the "R ^a number of C atoms that are connected via a straight chain group of Z" 2, similarly, C ^3, The chain in which the ZC repetition is completed in C ⁴ and C ⁵ is 3, 4 and 5, respectively, "the number of C atoms connected in a straight chain through the Z group in R ^a ". Further, as is clear from the above formula, ^a plurality of ZC chains exist in R ^a , but they need not all be the same length, but may be arbitrary lengths.

In a preferred form, as shown below, " the number of C atoms connected in a straight chain through the Z group in R ^a " is one (left figure) or two (right) in all chains.

In one form, the number of C atoms connected in a straight chain through the Z group in R < ^a > is one or two, preferably one.

Wherein R ² represents -Y-SiR ⁵ _n R ⁶ _{3 -n} .

Y represents, independently at each occurrence, a divalent organic group.

In a preferred aspect, Y is C _{1- 6} alkylene _{group, - (CH 2) g '} -O- (CH 2) h' - ( wherein, g 'is an integer, for example of from 0 to 6, from 1 to 6 (CH ₂ ) _{i '} - (wherein i' is an integer of 0 to 6), and h 'is an integer of 0 to 6, for example, an integer of 1 to 6. These groups are, for example, fluorine atom, C _{1- 6} alkyl, C _{2- 6} alkenyl group and C are optionally _2- substituted by one or more substituents selected from ₆ alkynyl group.

In one aspect, Y is C _{1- 6} alkylene _{group, -O- (CH 2) h '} - or - phenylene - (CH _{2) i'} - may be. When Y is the above-mentioned group, the light resistance, in particular, the ultraviolet light resistance, can be higher.

And R < ⁵ > each independently represent a hydroxyl group or a hydrolyzable group at each occurrence.

The "hydrolyzable group" as used herein means a group capable of undergoing a hydrolysis reaction. Examples of the hydrolyzable group include -OR, -OCOR, -ON = C (R) ₂ , -N (R) ₂ , -NHR, halogen (wherein R is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms , And is preferably -OR (alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; and substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly a non-substituted alkyl group, is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but hydrolyzable groups may be generated by hydrolysis.

Preferably, R ⁵ is -OR (wherein R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably an ethyl group or a methyl group, particularly a methyl group).

And R < ⁶ > each independently represent a hydrogen atom or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group.

n independently represents an integer of 1 to 3, preferably 2 or 3, more preferably 3 for each (-Y-SiR ⁵ _n R ⁶ _{3 -n} ) unit.

And R < ³ > each independently represent a hydrogen atom or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group.

Wherein p is, independently at each occurrence, an integer of 0 to 3; q is, independently at each occurrence, an integer from 0 to 3; and r is an integer of 0 to 3, independently for each occurrence. Provided that the sum of p, q and r is 3.

In a preferred form, R ^{a '(unless} the R ^a' present, R ^a) terminal of the R ^a of the method, wherein q is preferably 2 or more, for example 2 or 3, more preferably 3.

Wherein R ^b represents, independently at each occurrence, -Y-SiR ⁵ _n R ⁶ _{3 -n} . Here, Y, R ⁵ , R ⁶ and n have the same meanings as those described for R ² above.

In the above formulas, R ^c represents, independently at each occurrence, a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group.

Wherein k is, independently at each occurrence, an integer of 0 to 3; l is independently at each occurrence an integer of 0 to 3; m is an integer of 0 to 3 independently for each occurrence. The sum of k, l and m is 3.

In one form, at least one k is 2 or 3, preferably 3.

In one form, k is 2 or 3, preferably 3.

In one form, l is 2 or 3, preferably 3.

At least one q in the formulas (1a) and (1b) is 2 or 3, or at least one l is 2 or 3. That is, wherein at least two ^{_{-Y-SiR 5 n R 6 3}} -n group is present.

In the perfluoro (poly) ether group-containing silane compound represented by the above formula (1a) or (1b), the average molecular weight of the Rf-PFPE moiety is not particularly limited, but is preferably 500 to 30,000, More preferably from 2,000 to 10,000.

The perfluoro (poly) ether group-containing silane compound of the present invention represented by the above formula (1a) or (1b) is not particularly limited and may have an average molecular weight of 5 × 10 ² to 1 × 10 ⁵ . Among these ranges, those having an average molecular weight of 2,000 to 32,000, more preferably 2,500 to 12,000 are preferable from the viewpoint of friction durability. In the present invention, " average molecular weight " refers to a number average molecular weight and " average molecular weight " is a value measured by ¹⁹ F-NMR.

The perfluoro (poly) ether group-containing silane compound represented by the formula (1a) or (1b) can be produced by combining known methods. For example, the compound represented by formula (1a ') wherein X is a divalent compound is not limited, but can be prepared as follows.

(Preferably allyl) and a halogen (preferably a halogen-containing group) to a polyhydric alcohol represented by HO-XC (YOH) _{3 wherein} X and Y are each independently a divalent organic group (Hal-XC (YOR-CH = CH ₂ ) _{3 wherein} Hal is a halogen such as Br and R is a divalent organic group such as an alkylene group) To obtain the expressed double bond-containing halide. Subsequently, a perfluoropolyether group-containing alcohol represented by the terminal halogen and R ^PFPE -OH (wherein R ^PFPE is a perfluoropolyether group-containing group) is reacted to obtain R ^PFPE- OXC (YOR -CH = CH ₂ ) ₃ . Subsequently, R ^PFPE- OXC (YOR-CH ₂ -CH ₂ -SiR ⁵ ₃ ) ₃ can be obtained by reacting the terminal -CH═CH ₂ with HSiCl ₃ and an alcohol or HSiR ⁵ ₃ .

The reaction conditions for producing the perfluoro (poly) ether group-containing silane compound of the present invention can be appropriately adjusted within a range suitable for those skilled in the art.

Next, the surface treatment agent of the present invention will be explained.

The surface treatment agent of the present invention contains at least one perfluoro (poly) ether group-containing silane compound represented by the formula (1a) or (1b).

The surface treatment agent of the present invention can impart water repellency, oil repellency, antifouling property, surface slipperiness, and friction durability to a substrate and is not particularly limited, but can be suitably used as an antifouling coating agent or a waterproof coating agent.

In one form, the compound represented by formula (1a) or formula (1b) contained in the surface treatment agent of the present invention is a compound wherein X is a divalent organic group and? And?

In one form, the compound represented by the formula (1a) or the formula (1b) included in the surface treatment agent of the present invention has l of 3 and n of 3.

In one form, the perfluoropolyether group-containing silane compound contained in the surface treatment agent of the present invention is represented by formula (1a).

The surface treatment agent may contain other components in addition to the compound represented by the formula (1a) or the formula (1b). Examples of such other components include, but are not limited to, fluoropolyether compounds (non-reactive), preferably perfluoro (poly) ether compounds (Hereinafter referred to as " silicone oil "), a catalyst, and the like, which can be understood as silicone oil.

The fluorine-containing oil is not particularly limited, and examples thereof include a compound represented by the following general formula (3) (perfluoro (poly) ether compound).

Wherein, R ²¹ is 1 or represents a (perfluoroalkyl group of preferably C _1-16) alkyl group of C _1-16 which may be substituted by further fluorine atoms, R ²² is one or more 1 C _1-16 alkyl that may be substituted by fluorine atoms (preferably a C _1-16 perfluoroalkyl group), represents a fluorine atom or a hydrogen atom, R ²¹ and R ²² are each independently more preferably , C _1-3 perfluoroalkyl group.

a ', b', c 'and d' each represent the number of four kinds of repeating units of perfluoro (poly) ether constituting the main skeleton of the polymer and are independently an integer of 0 to 300, , b ', c' and d 'is at least 1, preferably from 1 to 300, more preferably from 20 to 300. The order of existence of each repeating unit enclosed in parentheses with subscripts a ', b', c ', or d' is arbitrary in the equation. Of these repeating _{units, - (OC 4 F 8)} - it is _{- (OCF 2 CF 2 CF 2} CF 2) -, - (OCF (CF 3) CF 2 CF 2) -, - (OCF 2 CF (CF 3) _{CF 2) -, - (OCF} 2 CF 2 CF (CF 3)) -, - (OC (CF 3) 2 CF 2) -, - (OCF 2 C (CF 3) 2) -, - (OCF (CF _{3) CF (CF 3))} -, - (OCF (C 2 F 5) CF 2) - and _{- (OCF 2 CF (C 2} F 5)) - of which one, but even if, preferably, - (OCF ₂ CF ₂ CF ₂ CF ₂ ) -. - (OC ₃ F ₆₎ - is _{- (OCF 2 CF 2 CF 2} ) -, - (OCF (CF 3) CF 2) - and _{- (OCF 2 CF (CF 3} )) - which would be least, preferably of Is - (OCF ₂ CF ₂ CF ₂ ) -. - (OC ₂ F ₄ ) - may be - (OCF ₂ CF ₂ ) - and - (OCF (CF ₃ )) -, preferably - (OCF ₂ CF ₂ ) -.

Examples of the perfluoro (poly) ether compound represented by the general formula (3) include compounds represented by any one of the following general formulas (3a) and (3b) .

R ²¹ - (OCF ₂ CF ₂ CF ₂ ) _{b "} -R ²² (3a)

^{_{R 21 - (OCF 2 CF 2}} CF 2 CF 2) a "- (OCF 2 CF 2 CF 2) b" - (OCF 2 CF 2) c "- (OCF 2) d" -R 22 ... (3b)

In these formulas, R ²¹ and R ²² are as defined above; B "in the formula (3a) is an integer of not less than 1 but not more than 100; and in the formula (3b), a" and b "are each independently an integer of 0 or more and 30 or less, c" and d " Is an integer in the range of 1 to 300. The order of existence of each repeating unit enclosed in parentheses with subscripts a, b, c, and d is arbitrary in the equation.

The fluorine-containing oil may have an average molecular weight of 1,000 to 30,000. Thereby, a high surface slip property can be obtained.

In the surface treatment agent of the present invention, the fluorine-containing oil is added in an amount of, for example, from 0 to 500 parts by mass, more preferably from 0 to 500 parts by mass, per 100 parts by mass of the total PFPE- Preferably from 0 to 400 parts by mass, more preferably from 25 to 400 parts by mass.

The compound represented by formula (3a) and the compound represented by formula (3b) may be used alone or in combination. It is preferable to use the compound represented by the general formula (3b) rather than the compound represented by the general formula (3a) since a higher surface slip property can be obtained. When these are used in combination, the mass ratio of the compound represented by formula (3a) to the compound represented by formula (3b) is preferably 1: 1 to 1:30, more preferably 1: 1 to 1:10 desirable. According to such a mass ratio, it is possible to obtain a surface treatment layer excellent in balance between surface slip and friction durability.

In one form, the fluorine-containing oil comprises one or more compounds represented by the general formula (3b). In this form, the mass ratio of the compound represented by Formula (1a) or Formula (1b) to the compound represented by Formula (3b) in the surface treatment agent is preferably 4: 1 to 1: 4.

In one preferred form, the surface treatment agent of the present invention is a compound represented by formula (1a) or (1b) wherein PFPE is - (OCF ₂ CF ₂ CF ₂ ) _b - (b is an integer of 1 to 200) Include compounds represented by the formula (3b). By using such a surface treatment agent and forming a surface treatment layer by a wet coating method or a vacuum deposition method, preferably a vacuum deposition method, excellent surface slip and friction durability can be obtained.

In one more preferred form of the surface treatment agent of the present invention PFPE is - (wherein _{- (OC 4 F 8) a} - (OC 3 F 6) b - (OC 2 F 4) c - (OCF 2) d , a and b each independently represent an integer of 0 or more and 30 or less, preferably 0 or more and 10 or less, and c and d are each independently an integer of 1 to 200, and the sum of a, b, c and d is 10 And an integer of not less than 200. The order of existence of each repeating unit attached with the suffixes a, b, c, or d and parenthesized is optional in the formula) and a compound represented by the formula (3b) . By using such a surface treatment agent and forming a surface treatment layer by a wet coating method or a vacuum deposition method, preferably by vacuum deposition, more excellent surface slip and friction durability can be obtained.

In these forms, the average molecular weight of the compound represented by the formula (3a) is preferably 2,000 to 8,000.

In these forms, the average molecular weight of the compound represented by the formula (3b) is preferably 2,000 to 30,000. The average molecular weight of the compound represented by the formula (3b) is preferably from 8,000 to 30,000 when the surface-treated layer is formed by a dry coating method, for example, a vacuum deposition method, and is preferably carried out by a wet coating method, In the case of forming the surface treatment layer, it is preferably 2,000 to 10,000, especially 3,000 to 5,000.

In a preferred form, when the surface treatment layer is formed by the vacuum vapor deposition method, the average molecular weight of the fluorine-containing oil may be larger than the average molecular weight of the compound represented by the formula (1a) or (1b). By having the average molecular weight of the compound represented by the formula (1a) or the formula (1b) and the fluorine-containing oil, more excellent surface slip and friction durability can be obtained.

In another aspect, the fluorine-containing oil may be a compound represented by the general formula Rf'-F (wherein Rf 'is a perfluoroalkyl group having _{5 to 16} carbon atoms). The compound represented by Rf'-F is preferable in that a high affinity with a compound represented by the above formula (1a) or (1b) in which Rf is a C _1-16 perfluoroalkyl group can be obtained.

The fluorine-containing oil contributes to improving the surface slip property of the surface treatment layer.

As the silicone oil, for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used. The straight-chain silicone oil may be so-called straight silicone oil or modified silicone oil. Examples of the straight silicone oil include dimethyl silicone oil, methylphenyl silicone oil and methylhydrogen silicone oil. Examples of the modified silicone oil include those obtained by modifying a straight silicone oil with an alkyl, an aralkyl, a polyether, a higher fatty acid ester, a fluoroalkyl, an amino, an epoxy, a carboxyl, an alcohol or the like. The cyclic silicone oil includes, for example, cyclic dimethylsiloxane oil and the like.

In the surface treatment agent of the present invention, such a silicone oil is added in an amount of, for example, from 0 to 300 parts by weight, based on the total 100 parts by mass (in the case of two or more kinds thereof, the total amount thereof) of the PFPE- , Preferably 50 to 200 parts by mass.

The silicone oil contributes to improving the surface slip property of the surface treatment layer.

Examples of the catalyst include an acid such as acetic acid and trifluoroacetic acid, a base such as ammonia, triethylamine and diethylamine, a transition metal such as Ti, Ni, Sn, ) And the like.

The catalyst promotes the hydrolysis and dehydration condensation of the PFPE-containing silane compound of the present invention and promotes the formation of the surface treatment layer.

As other components, for example, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltriacetoxysilane and the like may be used in addition to the above- .

The surface treatment agent of the present invention can be made into a pellet by impregnating a porous material, for example, a porous ceramic material, a metal fiber, for example, a steel wool into a surface hardened. The pellets can be used, for example, for vacuum deposition.

Next, the article of the present invention will be described.

The article of the present invention comprises a substrate and a layer (surface treatment layer) formed of the PFPE-containing silane compound or surface treatment agent of the present invention (hereinafter, simply referred to as " the surface treatment agent of the present invention " do. This article can be produced, for example, as follows.

First, a substrate is prepared. The substrate that can be used in the present invention may be, for example, a glass, a resin (natural or synthetic resin such as a general plastic material, or a plate, film or other form) (Construction material), ceramic, semiconductor (silicon, germanium, etc.), fiber (fabric, nonwoven fabric, etc.), fur, leather, wood, ceramics, .

For example, when the article to be manufactured is an optical member, the material constituting the surface of the substrate may be a material for optical members, such as glass or transparent plastic. Further, when the article to be produced is an optical member, a layer (or film) such as a hard coat layer or an antireflection layer may be formed on the surface (outermost layer) of the substrate. As the antireflection layer, either a single-layer antireflection layer or a multilayer antireflection layer may be used. Examples of the mineral available for the anti-reflection _{layer, SiO 2, SiO, ZrO 2} , _{TiO 2, TiO, Ti 2 O} 3, Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ , MgO, Y ₂ O ₃ , SnO ₂ , MgF ₂ , WO ₃ and the like. These inorganic substances may be used alone or in combination of two or more thereof (for example, as a mixture). In the case of forming a multilayer antireflection layer, it is preferable to use SiO ₂ and / or SiO _{2 as} the outermost layer. When the article to be manufactured is an optical glass part for a touch panel, a transparent electrode, for example, a thin film made of indium tin oxide (ITO) or indium zinc oxide may be provided on a part of the surface of a substrate (glass). The substrate may have an insulating layer, a pressure-sensitive adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating layer, a polarizing film, an uppermost film and a liquid crystal display module .

The shape of the substrate is not particularly limited. The surface area of the substrate on which the surface treatment layer is to be formed may be at least a part of the surface of the substrate, and may be appropriately determined according to the use of the article to be produced, the specific specification, and the like.

As such a substrate, at least the surface portion thereof may be made of a material originally having a hydroxyl group. Examples of such a material include glass, metals (particularly, base metals), ceramics, semiconductors, etc. on which a natural oxide film or a thermally oxidized film is formed on the surface. A hydroxyl group can be introduced or increased on the surface of the substrate by carrying out a certain pretreatment to the substrate when the hydroxyl group is not sufficient even when it has a hydroxyl group such as a hydroxyl group or a resin. Examples of such pretreatment include plasma treatment (for example, corona discharge) and ion beam irradiation. Plasma treatment can be suitably used for introducing or increasing hydroxyl groups on the surface of a substrate and for purifying the substrate surface (for removing foreign substances and the like). As another example of such pretreatment, an interfacial adsorbent having a carbon-carbon unsaturated bonding group is formed in advance in the form of a monomolecular film on the surface of a substrate by the LB method (Langmuir-Blodgett method) or a chemisorption method, , And the like.

As such a base material, at least the surface portion thereof may be made of a material containing a silicon compound having at least one reactive group, for example, Si-H group, or an alkoxysilane.

Subsequently, a film of the above-mentioned surface treatment agent of the present invention is formed on the surface of such a base material, and this film is optionally post-treated, thereby forming a surface treatment layer with the surface treatment agent of the present invention.

The film formation of the surface treatment agent of the present invention can be carried out by applying the above surface treatment agent to the surface of the substrate so as to cover the surface. The coating method is not particularly limited. For example, a wet coating method and a dry coating method can be used.

Examples of the wet coating method include immersion coating, spin coating, flow coating, spray coating, roll coating, gravure coating and the like.

Examples of the dry coating method include evaporation (usually, vacuum evaporation), sputtering, CVD, and the like. Specific examples of the vapor deposition method (vacuum deposition method in general) include resistance heating, electron beam, high frequency heating using microwave, ion beam, and similar methods. Specific examples of the CVD method include plasma CVD, optical CVD, thermal CVD, and the like.

It is also possible to coat by an atmospheric plasma method.

When the wet coating method is used, the surface treatment agent of the present invention can be applied to the substrate surface after being diluted with a solvent. In view of the stability of the surface treatment agent of the present invention and the volatility of the solvent, the following solvents are preferably used: perfluoro aliphatic hydrocarbons having 5 to 12 carbon atoms (for example, perfluorohexane, perfluoromethylcyclohexane And perfluoro-1,3-dimethylcyclohexane); Polyfluoroaromatic hydrocarbons (e. G., Bis (trifluoromethyl) benzene); Polyfluoroaliphatic hydrocarbons (for example, C ₆ F ₁₃ CH ₂ CH ₃ (for example, Asahikawa (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1,1,2,2, 3,3,4-heptafluorocyclopentane (for example, Aurora (registered trademark) H manufactured by Nippon Zeon Co., Ltd.), hydrofluoroether (HFE) (for example, perfluoropropyl methyl ether (C ₃ F ₇ OCH ₃ ) (for example, Novec 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) (for example, commercially available from Sumitomo 3M Limited, Novec (trademark) 7100, manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ) (for example, Novec (trade name) 7200 manufactured by Sumitomo 3M Limited), perfluorohexylmethyl ether _{(C 2 F 5 CF (OCH} 3) C 3 F 7) ( for example, Sumitomo 3M Novec (TM) 7300 of the Co., Ltd.) alkyl perfluoroalkyl ethers such as (purple Lu A search may be alkyl groups and the alkyl group is a straight chain or branched), or _{CF 3 CH 2 OCF 2 CHF 2} ( for example, Asahi Glass right or wrong to manufactured the Asahi Clean (R) AE-3000)), etc. These Among them, hydrofluoroether is preferable, and perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) and / or perfluorobutyl ethyl ether ( C ₄ F ₉ OC ₂ H ₅ ) is particularly preferred.

When the dry coating method is used, the surface treating agent of the present invention may be directly applied by a dry coating method, or may be diluted with the above-mentioned solvent and then dried by a coating method.

The film formation is preferably carried out so that the surface treating agent of the present invention coexists with the catalyst for hydrolysis and dehydration condensation in the film. Conveniently, in the case of the wet coating method, a catalyst may be added to the diluting liquid of the surface treatment agent of the present invention immediately before the surface treating agent of the present invention is diluted with a solvent and then applied to the surface of the substrate. In the case of the dry coating method, the surface treatment agent of the present invention, which has been added with the catalyst, is directly subjected to vapor deposition (usually by vacuum evaporation), or a metal porous article such as iron or copper is impregnated with the catalyst of the present invention Deposition (usually, vacuum deposition) treatment may be performed using a phase material.

Any suitable acid or base may be used for the catalyst. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid and the like can be used. As the base catalyst, for example, ammonia, organic amines and the like can be used.

Then, the film is post-treated if necessary. This post-treatment is not particularly limited, but for example, water supply and dry heating may be performed sequentially, and more specifically, the following treatment may be carried out.

After the surface treatment agent of the present invention is formed on the substrate surface as described above, water is supplied to the film (hereinafter also referred to as " precursor film "). The method of supplying moisture is not particularly limited, and for example, a method of dew condensation or spraying of water vapor (steam) by the temperature difference between the precursor film (and substrate) and the ambient atmosphere may be used.

When moisture is supplied to the precursor film, it is considered that water acts on the hydrolyzable group bonded to Si of the (poly) ether group-containing silane compound in the surface treatment agent of the present invention, thereby rapidly hydrolyzing the compound.

The supply of water can be carried out, for example, in an atmosphere of 0 to 250 ° C, preferably 60 ° C or more, more preferably 100 ° C or more, preferably 180 ° C or less, more preferably 150 ° C or less have. By supplying water in such a temperature range, hydrolysis can proceed. The pressure at this time is not particularly limited, but can be easily set at normal pressure.

Then, the precursor film is heated on the surface of the substrate in a drying atmosphere exceeding 60 캜. The drying and heating method is not particularly limited and the precursor film together with the substrate may be heated at a temperature exceeding 60 캜, preferably exceeding 100 캜, for example, at a temperature of 250 캜 or lower, preferably 180 캜 or lower, It may be disposed under an atmosphere of unsaturated water vapor pressure. The pressure at this time is not particularly limited, but can be easily set at normal pressure.

If this is under such an atmosphere, between the PFPE-containing silane compound of the present invention group bonded to the Si after the hydrolysis of [R ¹ are both hydroxyl groups in the compound represented by any of the formulas (1a) or formula (1b) include those hydroxyl being. The same applies hereinafter). Also, between the compound and the substrate, the reaction rapidly occurs between a group bonded to Si after hydrolysis of the compound and a reactive group existing on the surface of the substrate, and when the reactive group present on the surface of the substrate is a hydroxyl group, dehydration and condensation are performed. As a result, a bond is formed between the PFPE-containing silane compound of the present invention and a bond is formed between the compound and the substrate.

The above water supply and drying heating may be performed continuously by using superheated water vapor.

The superheated steam is a gas obtained by heating the saturated water vapor to a temperature higher than the boiling point. The superheated steam is a gas obtained by heating at a temperature higher than the boiling point and at a temperature higher than 100 ° C under normal pressure and generally not higher than 250 ° C, for example, not higher than 180 ° C, It is a gas that has become unsaturated steam pressure by heating. When the substrate on which the precursor film is formed is exposed to superheated water vapor, condensation occurs on the surface of the precursor film due to the temperature difference between the superheated steam and the relatively low temperature precursor film, thereby supplying moisture to the precursor film. Finally, as the temperature difference between the superheated steam and the precursor film becomes smaller, the moisture on the surface of the precursor film vaporizes in a dry atmosphere by superheated steam, and the moisture content on the surface of the precursor film gradually decreases. The precursor film on the surface of the substrate contacts the superheated steam while the moisture content of the precursor film surface is lowered, that is, while the precursor film is in a dry atmosphere, and the precursor film is heated to the temperature of the superheated steam (at a temperature exceeding 100 캜 under atmospheric pressure) . Therefore, when superheated water vapor is used, water supply and dry heating can be continuously performed only by exposing the substrate on which the precursor film is formed to superheated water vapor.

The post-treatment can be carried out as described above. It should be noted that such a post-treatment can be carried out to further improve the friction durability, but it is not essential for manufacturing the article of the present invention. For example, the surface treatment agent of the present invention may be applied to the surface of the substrate and then left to stand alone.

As described above, the surface treatment layer derived from the film of the surface treatment agent of the present invention is formed on the surface of the substrate to produce the article of the present invention. The surface treatment layer thus obtained has both high surface slip properties and high friction durability. In addition to high friction durability, the surface treatment layer is excellent in water repellency, oil repellency, antifouling property (for example, preventing adhesion of contamination such as fingerprints), waterproofness ), And surface slip property (or lubrication, for example, wiping of contamination such as fingerprints and excellent touch on fingers) and the like, and can be suitably used as a functional thin film.

That is, the present invention also relates to an optical material having the cured product in the outermost layer.

As the optical material, various optical materials are preferably used in addition to optical materials related to displays and the like as exemplified later. Examples of the optical material include a cathode ray tube (CRT; for example, a personal computer monitor), a liquid crystal display, a plasma (E.g., a display, an organic EL display, an inorganic thin film EL dot matrix display, a rear projection display, a fluorescent display tube (VFD), a field emission display (FED) It was treated with a barrier film.

An article having a surface treatment layer obtained by the present invention is not particularly limited, but may be an optical member. Examples of optical members include: lenses such as glasses; PDP, LCD, etc., anti-reflective plate, polarizer plate, anti-glare plate; A touch panel sheet of a device such as a cellular phone, a portable information terminal, and the like; A disc surface of an optical disc such as a Blu-ray (registered trademark) disc, a DVD disc, a CD-R, or an MO; Optical fiber; The display surface of the watch, etc.

The article having the surface treatment layer obtained by the present invention may be a medical device or a medical material.

The thickness of the surface treatment layer is not particularly limited. In the case of the optical member, the thickness of the surface treatment layer is preferably in the range of 1 to 50 nm, 1 to 30 nm, and preferably 1 to 15 nm in view of optical performance, surface slipperiness, friction durability and antifouling property.

The products obtained by using the surface treatment agent of the present invention have been described in detail above. The use of the surface treatment agent of the present invention, the method of use, the method of producing the article, and the like are not limited to those exemplified above.

Example

The surface treating agent of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the present embodiment, four repeating units (CF ₂ O), (CF ₂ CF ₂ O), (CF (CF ₃ ) CF ₂ O), (CF ₂ CF ₂ CF ₂ O) and (CF ₂ CF ₂ CF ₂ CF ₂ O) are arbitrary.

Synthesis Example 1

To a 100 mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer, 4.62 g of NaH and 0.41 g of tetrabutylammonium bromide were charged. Then, 23 g of 1,3-bis (trifluoromethyl) benzene, And 10 g of pentaerythritol triallyl ether were added and stirred at 65 DEG C and then separated and purified to obtain 5.23 g of the following pentaerythritol triallyl ether bromo adduct (A).

ㆍ Pentaerythritol triallyl ether bromo adduct (A):

BrCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ C (CH ₂ OCH ₂ CH = CH ₂ ) ₃

Synthesis Example 2

Reflux condenser, a thermometer and an average composition in the four-necked flask installed with a stirrer _{100mL CF 3 O (CF 2 CF} 2 O) 20 (CF 2 O) 16 CF 2 CH 2 OH [ during the stage, the mixture (CF ₂ CF ₂ CF ₂ (CF ₂ O) and / or (CF ₂ CF ₂ CF ₂ O), which is represented by the following formula: 51 g of 1,3-bis (trifluoromethyl) benzene and 0.39 g of KOH were added, and the mixture was stirred at 70 占 폚. Subsequently, 3.60 g of the pentaerythritol triallyl ether bromo adduct (A) obtained in Synthesis Example 1 and 0.14 g of tetrabutylammonium bromide were added and stirred at 70 ° C, followed by separation and purification to obtain an allyl group To obtain 4.86 g of the following perfluoropolyether group-containing allyloxane (B).

Perfluoropolyether group-containing allyloxane (B):

CF ₃ O (CF ₂ CF ₂ O) ₂₀ (CF ₂ O) ₁₆ CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ C (CH ₂ OCH ₂ CH = CH ₂ ) ₃

Synthesis Example 3

Into a 50 mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer were added 3.33 g of the perfluoropolyether group-containing allyloxy compound (B) synthesized in Synthesis Example 2, 1.3 g of 1,3-bis (trifluoromethyl) benzene and 0.01 g of triacetoxymethylsilane were put in the flask and stirred for 30 minutes. Subsequently, a solution of 1.16 g of trichlorosilane and 0.03 ml of a xylene solution containing 2% of Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, followed by stirring at 60 ° C for 3 hours did. Thereafter, the volatile components were distilled off under reduced pressure, and a mixed solution of 0.13 g of methanol and 5.25 g of trimethyl orthoformate was added thereto. The mixture was stirred at 50 캜 and then separated and purified to obtain a perfluorosuccinic acid having a trimethoxysilyl group To obtain 3.12 g of polyether group-containing silane compound (C).

Perfluoropolyether group-containing silane compound (C):

_{CF 3 O (CF 2 CF 2} O) 20 (CF 2 O) 16 CF 2 CH 2 OCH 2 CH 2 CH 2 CH 2 OCH 2 C (CH 2 OCH 2 CH 2 CH 2 Si (OMe) 3) 3

Synthesis Example 4

A 100 mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer was charged with a perfluoropolyether-denatured alcohol represented by the average composition CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₂₀ CF ₂ CF ₂ CH ₂ OH , 45 g of 1,3-bis (trifluoromethyl) benzene, and 0.33 g of KOH were charged, and the mixture was stirred at 70 占 폚. Subsequently, 3.10 g of the pentaerythritol triallyl ether bromo adduct (A) obtained in Synthesis Example 1 and 0.12 g of tetrabutylammonium bromide were added, stirred at 70 ° C, and then separated and purified to obtain an allyl group To obtain 4.81 g of the following perfluoropolyether group-containing allyloxane (D).

- Perfluoropolyether group-containing allyloxane (D):

CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₂₀ CF ₂ CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ C (CH ₂ OCH ₂ CH = CH ₂ ) ₃

Synthesis Example 5

4.5 g of the perfluoropolyether group-containing allyloxane (D) synthesized in Synthesis Example 4, 1.5 g of 1,3-bis (trifluoromethyl) benzene, 8.87 g and 0.01 g of triacetoxymethylsilane were put in the flask and stirred for 30 minutes. Subsequently, 1.42 g of trichlorosilane and 0.04 ml of a xylene solution containing 2% of Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added, followed by stirring at 60 ° C for 3 hours did. Thereafter, the volatile components were distilled off under reduced pressure, and a mixed solution of 0.16 g of methanol and 6.44 g of trimethyl orthoformate was added thereto. The mixture was stirred at 50 캜 and then separated and purified to obtain a perfluorosuccinic acid having a trimethoxysilyl group To obtain 4.36 g of polyether group-containing silane compound (E).

Perfluoropolyether group-containing silane compound (E):

_{CF 3 CF 2 CF 2 O (} CF 2 CF 2 CF 2 O) 20 CF 2 CF 2 CH 2 OCH 2 CH 2 CH 2 CH 2 OCH 2 C (CH 2 OCH 2 CH 2 CH 2 Si (OMe) 3) 3

Synthesis Example 6

Perfluoro a reflux condenser, a thermometer and a 50mL four-neck flask installed with a stirrer containing group, polyether-allyloxy body _{CF 3 O (CF 2 CF 2} O) 20 (CF 2 O) 16 CF 2 C (OCH 2 CH = CH ₂ ) (CH ₂ CH = CH ₂ ) ₂ ) (the mixture also contains a trace amount of repeating units of (CF ₂ CF ₂ CF ₂ CF ₂ O) and / or (CF ₂ CF ₂ CF ₂ O) 5.0 g of 1,3-bis (trifluoromethyl) benzene and 0.01 g of triacetoxymethylsilane were added thereto, and the mixture was stirred for 30 minutes. Subsequently, 1.50 g of trichlorosilane and 0.05 ml of a xylene solution containing 2% of Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane were added, followed by stirring at 60 ° C for 3 hours did. Thereafter, the volatile components were distilled off under reduced pressure, and a mixed solution of 0.20 g of methanol and 7.0 g of trimethyl orthoformate was added thereto. The mixture was stirred at 50 캜 and then separated and purified to obtain a perfluorosuccinic acid having a trimethoxysilyl group To obtain 5.32 g of a polyether group-containing silane compound (F).

ㆍ Perfluoropolyether group-containing silane compound (F):

_{CF 3 O (CF 2 CF 2} O) 20 (CF 2 O) 16 CF 2 C [OCH 2 CH 2 CH 2 Si (OMe) 3] [CH 2 CH 2 CH 2 Si (OMe) 3] 2

Synthesis Example 7

A 50 mL four-necked flask equipped with a reflux condenser, a thermometer and a stirrer was charged with perfluoropolyether group-containing allyl oxide CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₂₀ CF ₂ CF ₂ C (OCH ₂ CH = CH ₂ ) (CH ₂ CH = CH ₂ ) ₂ ), 7.2 g of 1,3-bis (trifluoromethyl) benzene and 0.01 g of triacetoxymethylsilane, and the mixture was stirred for 30 minutes. Subsequently, 0.04 ml of a xylene solution containing 1.20 g of trichlorosilane and 2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, followed by stirring at 60 ° C for 3 hours did. Thereafter, the volatile components were distilled off under reduced pressure, and a mixed solution of 0.16 g of methanol and 5.6 g of trimethyl orthoformate was added thereto. The mixture was stirred at 50 캜 and then separated and purified to obtain a perfluorosuccinic acid having a trimethoxysilyl group To obtain 4.4 g of polyether group-containing silane compound (G).

ㆍ Perfluoropolyether group-containing silane compound (G):

CF ₃ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₂₀ CF ₂ CF ₂ C [OCH ₂ CH ₂ CH ₂ Si (OMe) ₃ ] [CH ₂ CH ₂ CH ₂ Si (OMe) ₃ ] ₂

Example 1

The surface treatment agent 1 was prepared by dissolving the compound (C) obtained in Synthesis Example 3 in hydrofluoroether (Noveb HFE7200, manufactured by 3M) to a concentration of 20 wt%.

The surface treatment agent 1 prepared above was vacuum-deposited on chemically tempered glass ("Gorilla" glass, thickness: 0.7 mm, made by Corning). The vacuum deposition was performed under the conditions of a pressure of 3.0 x 10 < ^-3 > Pa and a 7 nm silicon dioxide film was formed on the surface of the chemically tempered glass. Subsequently, (Containing 0.4 mg of the compound (C)] was deposited. Thereafter, the chemically tempered glass having a vapor-deposited film was left to stand for 24 hours in an atmosphere at a temperature of 20 캜 and a humidity of 65%.

Example 2

A surface treatment agent was prepared in the same manner as in Example 1 except that the compound (E) obtained in Synthesis Example 5 was used in place of the compound (C) to form a surface treatment layer.

Example 3

A surface treatment agent was prepared in the same manner as in Example 1 except that the compound (F) obtained in Synthesis Example 6 was used in place of the compound (C) to form a surface treatment layer.

Example 4

A surface treatment agent was prepared in the same manner as in Example 1 except that the compound (G) obtained in Synthesis Example 7 was used in place of the compound (C) to form a surface treatment layer.

Example 5

A surface treatment agent was prepared in the same manner as in Example 1 except that the following perfluoropolyether group-containing silane compound (H) was used in place of the compound (C) to form a surface treatment layer.

Perfluoropolyether group-containing silane compound (H):

_{CF 3 O (CF 2 CF 2} O) 20 (CF 2 O) 16 CF 2 C [OC (O) NHCH 2 CH 2 CH 2 Si (OMe) 3] [CH 2 CH 2 CH 2 Si (OMe) 3] ₂

Comparative Examples 1 to 3

A surface treatment agent was prepared in the same manner as in Example 1 except that the following Control Compounds 1 to 3 were used in place of Compound (C) to form a surface treatment layer.

ㆍ Control Compound 1

CF ₃ O (CF ₂ CF ₂ O) ₂₀ (CF ₂ O) ₁₆ CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

ㆍ Control Compound 2

(Wherein g is an integer of 1 to 6)

Control Compound 3

(Wherein g is an integer of 1 to 6)

ㆍ Friction durability evaluation

The static contact angle of water was measured on the surface treatment layer formed on the surface of the substrate in the above Examples and Comparative Examples. The static contact angle of water was measured with a contact angle measuring apparatus (manufactured by Kyowa Chemical Co., Ltd.) with 1 mu L of water.

First, as an initial evaluation, the static contact angle of water was measured (the number of times of friction was 0) in a state where nothing had yet contacted the surface after forming the surface treatment layer. Thereafter, as a friction durability evaluation, a steel wool friction durability evaluation was carried out. Specifically, the base material on which the surface treatment layer was formed was placed horizontally, and a steel wool (number # 0000, dimension 5 mm x 10 mm x 10 mm) was brought into contact with the exposed upper surface of the surface treatment layer, Thereafter, the steel wool was reciprocated at a speed of 140 mm / sec in a state where a load was applied. The static contact angle (degree) of water was measured every 2,500 reciprocations, and the evaluation was stopped when the measured value of the contact angle became less than 100 degrees. The results are shown in Table 1 (in the table, the symbol " - " is not measured).

As can be understood from the above results, Examples 1 to 5 using the perfluoropolyether group-containing silane compounds of the present invention having a plurality of Si (OMe) ₃ groups branched from the main chain carbon atoms, It was confirmed that the friction durability was improved as compared with Comparative Examples 1 to 3 in which the compound was used.

The present invention can be suitably used for forming a surface treatment layer on various substrates, particularly on the surface of an optical member which is required to have transparency.

Claims (28)

Formula (1a) or Formula (1b):

[Wherein:
Rf represents, independently at each occurrence, an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms;
PFPE is independently present at each occurrence of the formula:

A, b, c, and d are each independently an integer of 0 to 200, and the sum of a, b, c, and d is at least 1 and is in parentheses The order of existence of each repeating unit is arbitrary in the formula.)
≪ / RTI >
Each X independently represents a single bond or an organic group of 2 to 10 carbon atoms;
a is independently an integer of 1 to 9;
beta is an integer from 1 to 9;
R ^a independently for each occurrence represents -Z-CR ¹ _p R ² _q R ³ _r ;
Z represents, at each occurrence independently of each other, an oxygen atom or a divalent organic group;
R ¹ represents each independently a, R ^{a ',} in each occurrence;
R ^{a '} has the same meaning as R ^a ;
Of R &^lt; a >, there are at most 5 C connected in a straight chain through the group Z;
R ² for each occurrence independently represents -Y-SiR ⁵ _n R ⁶ _{3 -n} ;
Y represents, independently at each occurrence, a divalent organic group;
R < ⁵ > independently at each occurrence represents a hydroxyl or hydrolyzable group;
R ⁶ represents, independently at each occurrence, a hydrogen atom or a lower alkyl group;
n is the (-Y-SiR ⁵ R ⁶ _{n 3 -n)} independently for each unit, an integer of 1 to 3;
R ³ represents, independently at each occurrence, a hydrogen atom or a lower alkyl group;
p is, independently at each occurrence, an integer from 0 to 3;
q is, independently at each occurrence, an integer from 0 to 3;
r is, independently at each occurrence, an integer from 0 to 3;
R ^b for each occurrence independently represents -Y-SiR ⁵ _n R ⁶ _{3 -n} ;
R ^c each independently represent a hydrogen atom or a lower alkyl group at each occurrence;
k is, independently for each occurrence, an integer from 0 to 3;
l is independently at each occurrence an integer of 0 to 3;
m is, independently at each occurrence, an integer from 0 to 3;
With the proviso that at least one q is 2 or 3, or at least one l is 2 or 3. < RTI ID = 0.0 >
(Poly) ether group-containing silane compound. The perfluoro (poly) ether group-containing silane compound according to claim 1, wherein 1 is 3. The perfluoro (poly) ether group-containing silane compound according to claim 1 or 2, wherein Rf is a perfluoroalkyl group having 1 to 16 carbon atoms. 4. The method according to any one of claims 1 to 3, wherein the PFPE is one of the following formulas (i) to (iv):

[Wherein b represents an integer of 1 to 200]

[Wherein b represents an integer of 1 to 200]

Wherein each of a and b is independently an integer of 0 to 30, c and d are each independently an integer of 1 to 200, and each repeating unit in parentheses, with subscripts a, b, c, or d, The order of existence is arbitrary in the equation.]
or

Wherein R ⁸ is OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , or a combination of 2 or 3 groups independently selected from these groups;
n "is an integer of 2 to 100.]
(Poly) ether group-containing silane compound. The perfluoro (poly) ether group-containing silane compound according to any one of claims 1 to 4, wherein X is a divalent organic group and? And? 6. The compound according to claim 5, wherein X is each independently - (R ³¹ ) _{p '} - (X ^a ) _q' -
[Wherein:
R ³¹ independently represents a single bond, - (CH ₂ ) _{s '} - (wherein s' is an integer of 1 to 20) or o-, m- or p-phenylene group;
X ^a represents - (X ^b ) _{l '} -, wherein 1' represents an integer of 1 to 10;
X ^b are each independently at each occurrence -O-, -S-, o-, m- or p-phenylene group, -C (O) O-, -Si (R ³³ ) ₂ -, - (R ³³ ) ₂ O) _{m '} -Si (R ³³ ) ₂ - (wherein m' is an integer of 1 to 100), -CONR ³⁴ -, -O-CONR ³⁴ -, -NR ³⁴ - CH ₂ ) _{n '} - (wherein n' is an integer of 1 to 20);
R ³³ is independently at each occurrence, phenyl, C _{1- 6} alkyl or C _{1- 6} represents an alkoxy group;
R ³⁴ is independently at each occurrence, represents a hydrogen atom, a phenyl group or a C _{1- 6} alkyl group;
p 'is 0, 1 or 2;
q 'is 0 or 1;
Wherein at least one of p 'and q' is 1 or more, the order of existence of each repeating unit in which p 'or q' is attached and is enclosed in parentheses is arbitrary in the formula;
R ³¹ and X ^a being optionally is substituted with one or more substituents selected from alkyl groups with a fluorine atom, C _{1- 3} alkyl and C _{1- 3} fluoro.]
(Poly) ether group-containing silane compound. 7. The compound according to claim 5 or 6, wherein each X is independently:

(Poly) ether group-containing silane compound selected from the group consisting of perfluoro (poly) ether group-containing silane compounds. The perfluoro (poly) ether group-containing silane compound according to any one of claims 1 to 4, wherein X is each independently an organic group having from 3 to 10 carbon atoms. 9. A compound according to claim 8, wherein X is each independently:

[Wherein, in each of the groups, at least one of T represents at least one of the following groups bonded to PFPE in the formulas (1a) and (1b)

Lt; / RTI >
At least one of the other T's is - (CH ₂ ) _n - (n is an integer from 2 to 6) bonded to -CR ^a _k R ^b ₁ R ^c _m in formulas (1a) and (1b) Each independently represent a methyl group, a phenyl group or an alkoxy group having 1 to 6 carbon atoms,
R ⁴¹ each independently represents a hydrogen atom, a phenyl group, an alkoxy group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms,
R ⁴² each independently represents a hydrogen atom, a C _1-6 alkyl group or a C _1-6 alkoxy group.
(Poly) ether group-containing silane compound selected from the group consisting of perfluoro (poly) ether group-containing silane compounds. To claim 1, wherein A method according to any one of items 9, Y is C _{1- 6} alkylene _{group, - (CH 2) g '} -O- (CH 2) h' - ( wherein, g 'is from 0 to 6 (Poly) ether group which is an integer of 0 to 6, and - phenylene- (CH ₂ ) _{i '} - (wherein i' is an integer of 0 to 6) Silane compound. 11. The perfluoro (poly) ether group-containing silane compound according to any one of claims 1 to 10, wherein the Rf-PFPE portion has a number average molecular weight of 500 to 30,000. 12. The perfluoro (poly) ether group-containing silane compound according to any one of claims 1 to 11, having a number average molecular weight of 2,000 to 32,000. A surface treatment agent comprising at least one perfluoro (poly) ether group-containing silane compound represented by formula (1a) and / or formula (1b) according to any one of claims 1 to 12. The surface treatment agent according to claim 13, further comprising one or more other components selected from a fluorine-containing oil, a silicone oil and a catalyst. 15. The process according to claim 14, wherein the fluorine-containing oil is represented by the formula (3):

[Wherein:
R ²¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
R ²² represents an alkyl group, a fluorine atom or a hydrogen atom of 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
a ', b', c 'and d' each represent the number of four kinds of repeating units of perfluoro (poly) ether constituting the main skeleton of the polymer and are independently an integer of 0 to 300, , b ', c' and d 'are at least 1, and the order of existence of each repeating unit in parentheses is given by subscripts a', b ', c' or d '.
Wherein R < 1 > 16. The process according to claim 14 or 15, wherein the fluorine-containing oil is a compound represented by the formula (3a) or (3b):

[Wherein:
R ²¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
R ²² represents an alkyl group, a fluorine atom or a hydrogen atom of 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
In the formula (3a), b "is an integer of 1 or more and 100 or less;
A "and b" each independently represent an integer of 0 or more and 30 or less; c "and d" are independently integers of 1 or more and 300 or less;
The order of existence of each repeating unit enclosed in parentheses with subscripts a, b, c, or d is optional in the equation.]
Wherein R < 1 > The surface treatment agent according to claim 16, which comprises at least one compound represented by at least formula (3b). The method according to claim 16 or 17, wherein at least one perfluoro (poly) ether group-containing silane compound represented by formula (1a) or formula (1b) described in any one of claims 1 to 12 And a compound represented by the formula (3b) in a weight ratio of 4: 1 to 1: 4. 19. The surface treatment agent according to any one of claims 16 to 18, wherein the compound represented by the formula (3a) has a number average molecular weight of 2,000 to 8,000. The surface treatment agent according to any one of claims 16 to 19, wherein the compound represented by the formula (3b) has a number average molecular weight of 2,000 to 30,000. 21. The surface treatment agent according to any one of claims 16 to 20, wherein the compound represented by the formula (3b) has a number average molecular weight of 8,000 to 30,000. 22. The surface treatment agent according to any one of claims 13 to 21, further comprising a solvent. 23. The surface treatment agent according to any one of claims 13 to 22, which is used as an antifouling coating agent or a waterproof coating agent. 24. The surface treatment agent according to any one of claims 13 to 23, which is for vacuum deposition. A pellet containing the surface treatment agent according to any one of claims 13 to 24. And a layer formed of the surface treatment agent according to any one of claims 13 to 24 or a compound according to any one of claims 1 to 12 on the surface of the substrate. 27. The article of claim 26, wherein the article is an optical member. 27. The article of claim 26, wherein the article is a display.